离子液体电沉积CuIn_xGa_(1-x)Se_2薄膜(英文)

采用循环伏安法(CV)对离子液体Reline中三元CuCl2+InCl3+SeCl4体系和四元CuCl2+InCl3+GaCl3+SeCl4体系的电化学行为进行了研究。研究表明,In3+并入三元CIS(Cu-In-Se)薄膜体系和Ga3+并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径:一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu1.00In0.78Ga0.27Se2.13的薄膜。     

Ga和Cu/In衬底上电沉积金属Ga

在酸性水溶液中,分别在金属Ga和Cu/In衬底上进行了Ga电沉积的研究。用循环伏安法研究了导电盐、pH值对电沉积Ga的影响。系统研究了Ga的沉积过程,发现Ga会逐渐向薄膜内部扩散,在Cu/In界面上与CuIn合金反应生成CuGa₂合金。针对Cu/In薄膜和Ga薄膜是活泼金属的特点,在溶液中加入三乙醇胺有效地保护了Cu/In薄膜和Ga金属薄膜不被氧化,并且提高了Ga沉积的电流效率。在Cu/In薄膜上制备出了均匀光亮的金属Ga薄膜。对电沉积出Cu-In-Ga预置层进行了硒化处理,得到了质量较好的Cu(In_1-xGa_x)Se₂(CIGS)薄膜,并制备了太阳电池。电池效率达到了9.42%。     

CuInSe_2薄膜的电化学沉积及其形成机理

采用电化学沉积法制备了太阳电池用CuInSe2薄膜.利用循环伏安法(CV)、X射线能谱(EDS)和X射线衍射技术(XRD)研究了电沉积过程中CuInSe2的形成机理,并研究了制备工艺对膜层成分、形貌和物相结构的影响.研究结果表明,铟进入固相是通过In3+受Cu3Se2诱导作用欠电势还原或者In3+与H2Se反应这两种途径实现;先沉积的Cu3Se2与新生成的铟或铟硒化合物反应最后生成CuInSe2.在阴极电位为-0.58~-0.9 V(vs.SCE)时出现了不随电位变化的极限还原电流,在该电位范围内进行电沉积获得了化学计量组成稳定可控且相对致密平整的CuInSe2薄膜.电沉积的CuInSe2薄膜经真空退火处理后结晶质量得到明显改善.     

n型Bi_2Te_(3-y)Se_y温差电材料薄膜的电化学制备及表征

采用电化学控电位的方法在不锈钢基片上电沉积制备了Bi2Te3-ySey温差电材料薄膜。研究了电沉积溶液中硒含量与薄膜中硒含量的关系,考察了不同沉积电位对电沉积Bi2Te3-ySey薄膜的温差电性能的影响,并采用ESEM、EDS、XRD等方法对电沉积薄膜的形貌、成分及结构进行了分析。结果表明,在含有Bi3 、HTeO2 和Se4 的电沉积溶液中,采用电化学沉积的方法,可实现铋、碲、硒三元共沉积,生成Bi2Te3-ySey半导体化合物。改变电沉积溶液组成,可控制Bi2Te3-ySey化合物中硒的掺杂浓度。-0.04V沉积电位下制备的Bi2Te3-ySey薄膜较平整、致密,组成为Bi2Te2.7Se0.3。退火处理可提高电沉积Bi2Te3-ySey薄膜的塞贝克系数,且控制沉积电位为-0.04V下制备的Bi2Te3-ySey薄膜退火后的塞贝克系数为-123μV·K-1。     

离子液体电沉积CuInxGa1-xSe2薄膜

采用循环伏安法(CV)对离子液体Reline中三元CuCl₂+InCl₃+SeCl₄体系和四元CuCl₂+InCl₃+GaCl₃+SeCl₄体系的电化学行为进行了研究。研究表明,In³⁺并入三元CIS(Cu-In-Se)薄膜体系和Ga³⁺并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径：一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu_1.00In_0.78Ga_0.27Se_2.13的薄膜。     

激光刻蚀模板中电沉积特殊结构CIGS薄膜

本文利用激光刻蚀模板,在水溶液中电沉积制备金属铜薄膜,讨论了温度、电流、硫酸铜浓度对薄膜形貌的影响. 采用SEM对制备的铜薄膜进行表征,结果表明在沉积温度为30 ℃,沉积电流为4 A·dm^-2(表观工作电流密度),硫酸铜浓度在20 ~ 50 g·L^-1的水溶液中电沉积可以得到中空馒头状和开口碗状结构的铜薄膜. 利用激光刻蚀模板,在离子液体1-丁基-3-甲基咪唑三氟甲磺酸盐([BMI][TfO]) - 30 Vol%丙醇混合电解质中电沉积CIGS薄膜,研究了沉积电势、沉积时间对薄膜形貌的影响. SEM观察发现,在沉积电势为-1.8 V,沉积时间为1.5 h条件下电沉积可以得到近似柱状的簇状花束样的CIGS薄膜, 电沉积铜后再进一步电沉积CIGS,得到了均匀有序的鼓包柱状结构的Cu/CIGS复合薄膜. 用恒电势方波法对制备的薄膜真实表面积进行测试,计算结果表明,与无模板电沉积制备的CIGS薄膜相比,激光刻蚀模板法制备的Cu/CIGS复合薄膜的表面积提高了约8倍.     

以乙醇作溶剂电沉积制备CIGS薄膜

利用恒电位电沉积法在以乙醇为溶剂的溶液中制备了铜铟镓硒(CIGS)薄膜.并采用扫描电子显微镜(SEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)和紫外-可见-近红外(UV-VIS-NIR)分光光度计分别对薄膜的形貌、成分、晶体结构和吸收特性进行了表征.结果表明在-1.6V(相对于饱和甘汞电极电位)工作电位下沉积的薄膜经450°C退火后能够形成形貌均匀致密、结晶性良好、带隙约为1.17eV的黄铜矿结构CuIn0.7Ga0.3Se2薄膜.实验过程中发现,以乙醇为溶剂可以有效避免在水溶液中出现的析氢现象,减小了沉积电位的限制.     

Cu2ZnSn(S,Se)4薄膜太阳电池研究进展

CdTe和Cu(In,Ga)(S,Se)₂ (CIGSSe)光吸收材料在新型化合物半导体太阳电池研究中占据着主导地位。尽管CdTe和CIGS太阳电池拥有较高的转换效率和先进的技术,但是仍存在着一些问题,如所用材料中的元素地壳丰度低或有毒,这阻碍了其未来的大规模应用。近年来,由于Cu₂ZnSn(S,Se)₄ (CZTSSe)薄膜太阳电池使用的元素地壳含量丰富且环境友好,逐渐成为了研究的热点。CZTSSe光吸收材料被认为能够取代CdTe和CIGS成为下一代光伏技术的潜力材料。基于此,本文将简单介绍CZTSSe材料的结构、性质和制备方法。重点阐述CZTSSe材料的组装技术和沉积方法的发展和优势,如基于真空的沉积方法和基于溶液的沉积方法,简述其优缺点。此外,本文对CZTSSe组装和CZTSSe纳米晶制备方法的最新研究进展也进行了总结。最后,对CZTSSe光伏技术的一些限制因素进行了分析,并对CZTSSe薄膜电池未来的研究前景进行了展望。     

p型Se的电沉积及其转化为n型CdSe的机理研究

利用线性电位扫描光伏安法等技术研究钛基体上Se半导体薄膜的电化学形成及转化过程.实验结果表明,在H_2SeO_3溶液中进行电沉积可获得p型Se薄膜,它可在酸性CdSO_4溶液中阴极转化为n型CdSe.讨论了Se的电沉积动力学及其转化为CdSe的可能机理.所述原理可望用于p-n异质结的电化学制备.     

CdSe电沉积层的组成及形成机理

伏安曲线和现场光电流测定用于研究在钛基体上阴极电沉积形成Cdse薄膜的机理. XPS实验表明, CdSe沉积层的组成与沉积电位、沉积时间和溶液组成有关.在0.1 mol·L~(-1)CdSO_4+4 mmol·L~(-1)H_2SeO_3+0.2 mol·L~(-1) H_2SO_4溶液中, 当电位比-0.50 V正时生成富Se层, 而当电位比-0.70 V还负时生成富Cd层. 在-0.69 V下沉积, 沉积层的Se/Cd计量比接近1.1. 在同一电位下, 若提高H_2Se0_3浓度, 则沉积物中Se的含量增多. 实验结果表明, CdSe电沉积因条件不同遵循两种不同的机理, 据此讨论了克服Se/Cd比大于1的可能措施。     

Application of ICP-OES to the determination of CuIn<Subscript>1−x</Subscript>Ga<Subscript>x</Subscript>Se<Subscript>2</Subscript> thin films used as absorber materials in solar cell devices

CuIn_1–xGa_xSe₂ [CIGS; x=Ga/(In+Ga)] thin films are among of the best candidates as absorber materials for solar cell applications. The material quality and main properties of the polycrystalline absorber layer are critically influenced by deviations in the stoichiometry, particularly in the Cu/(In+Ga) atomic ratio. In this work a simple, sensitive and accurate method has been developed for the quantitative determination of these thin films by inductively coupled plasma optical emission spectrometry (ICP-OES). The proposed method involves an acid digestion of the samples to achieve the complete solubilization of CIGS, followed by the analytical determination by ICP-OES. A digestion procedure with 50% HNO₃ alone or in the presence of 10% HCl was performed to dissolve those thin films deposited on glass or Mo-coated glass substrates, respectively. Two analytical lines were selected for each element (Cu 324.754 and 327.396 nm, Ga 294.364 and 417.206 nm, In 303.936 and 325.609 nm, Se 196.090 and 203.985 nm, and Mo 202.030 and 379.825 nm) and a study of spectral interferences was performed which showed them to be suitable, since they offered a high sensitivity and no significant inter-element interferences were detected. Detection limits for all elements at the selected lines were found to be appropriate for this kind of application, and the relative standard deviations were lower than 1.5% for all elements with the exception of Se (about 5%). The Cu/(In+Ga) atomic ratios obtained from the application of this method to CIGS thin films were consistent with the study of the structural and morphological properties by X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Design of energy band alignment at the Zn(1-x)Mg(x)O/Cu(In,Ga)Se2 interface for Cd-free Cu(In,Ga)Se2 solar cells

The electronic band structure at the Zn(1-x)Mg(x)O/Cu(In(0.7)Ga(0.3))Se(2) interface was investigated for its potential application in Cd-free Cu(In,Ga)Se(2) thin film solar cells. Zn(1-x)Mg(x)O thin films with various Mg contents were grown by atomic layer deposition on Cu(In(0.7)Ga(0.3))Se(2) absorbers, which were deposited by the co-evaporation of Cu, In, Ga, and Se elemental sources. The electron emissions from the valence band and core levels were measured by a depth profile technique using X-ray and ultraviolet photoelectron spectroscopy. The valence band maximum positions are around 3.17 eV for both Zn(0.9)Mg(0.1)O and Zn(0.8)Mg(0.2)O films, while the valence band maximum value for CIGS is 0.48 eV. As a result, the valence band offset value between the bulk Zn(1-x)Mg(x)O (x = 0.1 and x = 0.2) region and the bulk CIGS region was 2.69 eV. The valence band offset value at the Zn(1-x)Mg(x)O/CIGS interface was found to be 2.55 eV after considering a small band bending in the interface region. The bandgap energy of Zn(1-x)Mg(x)O films increased from 3.25 to 3.76 eV as the Mg content increased from 0% to 25%. The combination of the valence band offset values and the bandgap energy of Zn(1-x)Mg(x)O films results in the flat (0 eV) and cliff (-0.23 eV) conduction band alignments at the Zn(0.8)Mg(0.2)O/Cu(In(0.7)Ga(0.3))Se(2) and Zn(0.9)Mg(0.1)O/Cu(In(0.7)Ga(0.3))Se(2) interfaces, respectively. The experimental results suggest that the bandgap energy of Zn(1-x)Mg(x)O films is the main factor that determines the conduction band offset at the Zn(1-x)Mg(x)O/Cu(In(0.7)Ga(0.3))Se(2) interface. Based on these results, we conclude that a Zn(1-x)Mg(x)O film with a relatively high bandgap energy is necessary to create a suitable conduction band offset at the Zn(1-x)Mg(x)O/CIGS interface to obtain a robust heterojunction. Also, ALD Zn(1-x)Mg(x)O films can be considered as a promising alternative buffer material to replace the toxic CdS for environmental safety.     

Pulsed Laser Deposition ZnS Buffer Layers for CIGS Solar Cells

Polycrystalline ZnS films were prepared by pulsed laser deposition （PLD） on quartz glass substrates under different growth conditions at different substrate temperatures of 20, 200, 400, and 600 ℃, which is a suitable alternative to chemical bath deposited （CBD） CdS as a buffer layer in Cu（In,Ga）Se2 （CIGS） solar cells. X-ray diffraction studies indicate the films are polycrystalline with zinc-blende structure and they exhibit preferential orientation along the cubic phase β-ZnS （111） direction, which conflicts with the conclusion of wurtzite structure by Murali that the ZnS films deposited by pulse plating technique was polycrystalline with wurtzite structure. The Raman spectra of grown films show Al mode at approximately 350 cm^-1, generally observed in the cubic phase β-ZnS compounds. The planar and the cross-sectional morphology were observed by scanning electron microscopic. The dense, smooth, uniform grains are formed on the quartz glass substrates through PLD technique. The grain size of ZnS deposited by PLD is much smaller than that of CdS by conventional CBD method, which is analyzed as the main reason of detrimental cell performance. The composition of the ZnS films was also measured by X-ray fluorescence. The typical ZnS films obtained in this work are near stoichiometric and only a small amount of S-rich. The energy band gaps at different temperatures were obtained by absorption spectroscopy measurement, which increases from 3.2 eV to 3.7 eV with the increasing of the deposition temperature. ZnS has a wider energy band gap than CdS （2.4 eV）, which can enhance the blue response of the photovoltaic cells. These results show the high-quality of these substitute buffer layer materials are prepared through an all-dry technology, which can be used in the manufacture of CIGS thin film solar cells.     

掺钠钼电极在硒化铜铟镓(CIGS)太阳能薄膜电池应用

适量钠元素对铜铟镓硒薄膜生长具有促进作用,本文主要研究了掺钠钼电极特性及其对铜铟镓硒薄膜太阳能电池性能的影响。利用磁控溅射方法制备不同厚度的钼钠/钼(Mo Na/Mo)薄膜作为背电极,并在(Mo Na/Mo)薄膜电极上蒸镀铜铟镓硒(CIGS)薄膜,并利用单质硒源硒化处理后制备CIGS薄膜电池。SEM和XRD结果表明采用三层叠层Mo/Mo/Mo Na薄膜做电极的Mo Na容易被氧化,电阻率增加,采用四层叠层Mo/Mo/Mo Na/Mo薄膜电极方式有效降低电阻率,阻止Mo Na被氧化,CIGS晶粒较大且致密。在同一条件下,在不同Mo Na/Mo厚度电极上制备CIGS薄膜电池,80 nm Mo Na厚度上的CIGS薄膜电池效率达6.54%。     

Dynamic analysis on metal selenide electrodeposition

Based on the basic principles of kinetics and some reasonable assumptions about the electrodeposition process, a dynamic model for metal selenide electrodeposition (kink site selected model) was constructed. This model is of universal significance in realizing the compositional prediction and dynamic behavior analysis of deposited films for different main salt concentration ratios and was applied to the ternary Cu–In–Se system. For CuInSe₂ electrodeposition, in the Cu–Se system, the co-deposition of Cu and Se can be carried out within a large range of main salt concentration ratio; in the Cu–In system, the mole fraction of Cu in deposited thin films is always higher than that of Cu²⁺ in electrolyte, while in the In–Se system, the co-deposition of In and Se can be achieved only when the In³⁺ concentration is much higher than the H₂SeO₃ concentration. As for the compositional estimation of CuInSe₂, the predictive results of our dynamic model agree well with the experimental data. It is then found that by correcting the difference of kink site selectivity constants caused by the change of deposition potential, the error of the predictive results can be reduced.